Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
  • C07C43/29—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0803—Compounds with Si-C or Si-Si linkages
  • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings

Definitions

• the compounds in accordance with the present invention are ethynylphenoxy and ethynylthiophenoxy derivatives of diphenylhexafluoropropane which have the following formula:
• the compounds of the present invention are also useful as plasticizing diluents for use in processing high molecular weight thermoplastics. Curing of high molecular weight thermoplastics with the compounds of the present invention incorporated therein produces a cross-linked network within the thermoplastic to enhance the high temperature structural strength of the thermoplastic. As another feature of the present invention, the presence of flexible oxygen or sulfur linkages (X) between the hexafluoroisopropylidene groups and the ethynylphenyl groups, along with the large molecular distance between the ethynyl end groups yields polymers and copolymers having improved resistance to fracturing.
• X flexible oxygen or sulfur linkages
• FIG. 1 is a schematic representation of two alternate exemplary processes for preparing a preferred ethynylphenoxy derivative of diphenylhexafluoropropane in accordance with the present invention.
• FIG. 2 is a schematic representation of an exemplary process for preparing a preferred ethynylthiophenoxy derivative of diphenylhexafluoropropane in accordance with the present invention.
• a preferred compound is 2, 2-bis [4( 4-ethynylphenoxy)phenyl] hexafluoropropane where X is oxygen, R 1 and R 2 are hydrogen and R is ethynyl.
• Another preferred compound is 2, 2-bis [4-(4-ethynylphenylthio)phenyl]hexafluoropropane where X is sulfur, R 1 and R 2 are hydrogen and R is ethynyl.
• Exemplary preparation of these two preferred embodiments are as follows.
• the preparation of 2, 2-bis [4-( 4-ethynylphenoxy)phenyl]hexafluoropropane (5) is shown schematically in FIG. 1.
• the 2, 2-bis [4-( 4-ethynylphenoxy)phenyl]hexafluoropropane (5) can be made by two preferred synthesis routes. Each route involves preparation of 2, 2-bis [4( 4-iodophenoxy)phenyl]hexafluoropropane (2) followed by reaction with either 2-methyl-3-butyn-2-ol or ethynyltrimethysilane to produce the intermediates (3) and (4) respectively as shown in FIG. 1. Each of the two intermediates is then treated as discussed below to form the desired 2, 2-bis [4-( 4-ethynylphenoxy)phenyl] hexafluoropropane (5).
• EXAMPLE 1 This example illustrates the preparation of 2,2bis [4-( 4-ethynylphenoxy)phenyl]hexafluoropropane (5) in accordance with the present invention.
• Compound 2 was prepared by first placing 250 ml of concentrated hydrochloric acid in a 4-liter beaker. While being stirred mechanically, the acid was treated with 103.6 grams (0.2 mole) of 2, 2-bis [4-( 4-aminophenoxy)phenyl] hexafluoropropane (1) (available from Morton
• the physical properties for the compound (2) are: IR (KBr): 3170 (weak), 1620, 1585, 1515, 1485, and very strong absorption at 1300-1175 cm -1 ;
• Ethynyltrimethylsilane (8.760g, 89.39 mmoles) was added and the mixture was rapidly heated to 70°C over 5 minutes. At 60°C, a clear yellow solution was obtained. At 70°C, precipitation of the white triethylamine hydroiodide commenced. The reaction temperature was raised to 90-95°C over 10 minutes and maintained at that temperature range for 6 hours. After one hour, an unexpected decomposition of the palladium complex took place and the white precipitate took on a grey color. The slurry was then cooled, diluted with 100 ml of ether and filtered. The grey solid was washed with more ether and air-dried.
• This example illustrates the preparation of 2,2-bis[4-(4-ethynylphenylthio)phenyl] hexafluoropropane in accordance with the present invention.
• Compound 6 Preparation of 2 ,2-Bis (4-mercaptophenyl)hexafluoropropane (Compound 6): Compound 6 and related bis(benzenethiol) compounds are disclosed in co-pending patent application Serial No. 453,431, filed December 27, 1982 and assigned to the same assignee as the present invention. Compound 6 and the related compounds are prepared in a three-step process. In the first step, a bisphenol is reacted with N,N-dimethylthiocarbamoyl chloride in the presence of a base. Preferably, a 10% to 20% molar excess of the carbamoyl chloride to bisphenol is used in this reaction.
• the preferred temperature for the reaction is in the range of about 0°C to about 60°C at atmospheric pressure.
• the preferred time of reaction is in the range of about one to about two hours.
• a class of compounds called O-thiocarbamate esters is obtained.
• the O-thiocarbamate esters from the first step are heated at a temperature in the range of about 150°C to about 275°C for a period in the range of about one to about two hours and at atmospheric pressure, preferably under an inert atmosphere such as argon, to form a class of compounds called S-thiocarbamate esters.
• the rearrangement reaction is known by the general term "Smiles Rearrangement".
• the S-thiocarbamate esters from the second step are treated with a strong base such as potassium hydroxide in methanol, and then treated with a concentrated acid such as hydrochloric or nitric to form the desired bis(benzenethiol) .
• a strong base such as potassium hydroxide in methanol
• a concentrated acid such as hydrochloric or nitric
• the product mixture was diluted with three liters of water and extracted twice with an 80:20 benzene/hexane solution. The organic phase was evaporated under reduced pressure to obtain a solid crystalline residue. The residue was recrystallized from a 5:1 methanol/ benezene solution to obtain 125 grams of a product melting at about 209°-211°C.
• This product was the O-thiocarbamate ester of Bisphenol AF. Fifteen grams (0.3 mole) of the O-thiocarbamate ester of bisphenol AF was placed in a reaction vessel, and heated at 250°C under argon for one hour.
• Compound 8 was prepared by hydrogenating
• Compound 9 was prepared by treating Compound 8 with sodium nitrite followed by potassium iodide according to the general diazotization procedure described in
• Compounds in accordance with the present invention may be utilized to form homopolymers or they may be copolymerized with various other ethynylated monomers such as acetylene-terminated sulfones (ATS) and acetyleneterminated imides.
• ethynylated monomers such as acetylene-terminated sulfones (ATS) and acetyleneterminated imides.
• the amount of ethynylated monomers incorporated into the copolymer may be varied depending upon desired properties for the copolymer. Copolymers with from 1 to 99 weight percent ethynylated monomers are possible.
• the compounds may be used as plasticizing diluents in the preparation of various high temperature resins such as polyimides, polybenzothiazoles, polyquinolines, and polyquinoxalines.
• the compounds When used as a plasticizing diluent, the compounds are preferably added to the resins in amounts ranging from a few weight percent up to about 30 weight percent.
• the amount of the present compounds added as a plasticizer can be varied to achieve desired improvements during handling and processing of the resin along with desired reductions in brittleness of the final resin product.
• EXAMPLE 3 A homopolymer of 2, 2-bis [4-(4-ethynylphenoxy)phenyl] hexafluoropropane was prepared by heating a sample of the neat material from 52°C to 315°C in a button mold at the rate of 2-3°C per minute. The resulting button was cured at 316°C for 2 hours. The cured button had a glass transition temperature of approximately 333°C. The polymer was stable, i.e. exhibited no weight loss during thermogravimetric analysis up to temperatures of above 500°C. The cured button was also post-cured for a total of 24 hours at a temperature of 316°C. The resulting post-cured button had a glass transition temperature of about 370°C. EXAMPLE 4
• a copolymer of 1 part of 2,2-bis [4-( 4-ethynylphenoxy)phenyl] hexafluoropropane and 4 parts of an acetylene-terminated polyimide oligomer of the type described in U.S. Patent No. 4,438,273 at columns 9-10 with an average degree of polymerization (DP) of 15 was prepared by heating a sample of the mixture in a button mold from 52°C to 315°C at the rate 2°C per minute. The resulting button was cured at 316°C for 24 hrs. The cured button had a glass transition temperature of approximately 325°C, and thermogravimetric analysis showed no weight loss up to 500°C.
• a diphenyl hexafluoropropane compound having the formula:
• R, R 1 and R 2 are hydrogen or ethynyl.
• a polymer material consisting essentially of a homopolymer of a diphenylhexafluoropropane compound according to Claim 2.
• a copolymer consisting essentially of a diphenylhexafluoropropane compound according to Claim 1 copolymerized with an ethynylated monomer.
• a copolymer according to Claim 11 wherein the diphenylhexafluoropropane compound is a compound according to Claim 2.
• a high temperature resin which includes an effective amount of a plasticizing diluent, said plasticizing diluent being a diphenylhexafluoropropane compound according to Claim 1.
• said resin is a polyimide, a polybenzothiazole, a polyquinoline or a polyquinoxaline.
• a high temperature resin according to Claim 14 wherein said diphenylhexafluoropropane compound is a compound according to Claim 2.

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• Chemical Kinetics & Catalysis (AREA)
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• Polymers & Plastics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1984
  • 1984-09-04 US US06/647,000 patent/US4695655A/en not_active Expired - Lifetime
• 1985
  • 1985-07-05 EP EP85905011A patent/EP0192766B1/en not_active Expired
  • 1985-07-05 JP JP60504402A patent/JPS62500104A/ja active Granted
  • 1985-07-05 DE DE8585905011T patent/DE3565101D1/de not_active Expired
  • 1985-07-05 WO PCT/US1985/001272 patent/WO1986001504A1/en active IP Right Grant

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